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SYNTHESIS  OF  QUINIZARIN 


BY 


RALPH  WALDO  FOOLER 


THESIS 

FOR  THE 

DEGREE  OF  BACHELOR  OF  SCIENCE 

IN 


CHEMISTRY 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1921 


Digitized  by  the  Internet  Archive 

in  2016 


https://archive.org/details/synthesisofquiniOOfogl 


UNIVERSITY  OF  ILLINOIS 


)31\ 


192I 

00 

01 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 


ML£H__WALD  0_  _ PO  GLEB. 


ENTITLED 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF BaciieXQr__or__E.aJLeiiiie._iii_iloeials.trY 


Instructor  in  Charge 


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IliTRCPUGTIOE 

1 

HISTORICAL  PART 

E 

THEORETICAL  P;^RT 

12 

EXPERIIIERT^L  PART 

13 

SULIMARY  AEL  COECLUSIOE 

EO 

BIBLIOGRAPHY 

21 

ACMOWLEPGIvISilT 

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AGMOV/IEDGL'EUT 

The  author,  at  this  point,  ?/ishes  to  express  his  appreciation 
of  the  help  that  Doctor  Roger  Adams  has  been,  under  v/hom  this  v/ork 
has  been  done.  This  problem  selected  by  Doctor  Adams  has  proven 
very  profitable  and  interesting,  and  his  attentive  help  has  been 
of  great  assistance. 


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KTRODUOTTOK 

The  purpose  of  this  research  was  not  only  to  synthesize 
quinizarine,  but  also  to  prepare  intermediate  products  for  the 
indanthrene  series  of  vat  dyes.  It  is  true  most  of  these  prodonts 
have  been  prepared  by  one  method  or  another.  However,  using 
phthalic  anhydride  as  a starting  point , they  have  not  been  prepared 
by  the  condensation  reaction.  Although  the  constituents  used  in 
this  condensation  are  cheap,  therefore,  it  would  be  of  advantage 
to  prepare  the  intermediate  products  by  this  method. 

The  class  of  compoTinds  with  whi  ch  the  writer  dealt  are  in 
great  demand,  because  they  form  the  basis  of  all  the  indanthrene 
vat  dyes.  It  v/as  originally  hoped  that  the  v/riter  v/ould  be  able 
to  work  on  the  preparation  of  some  nev/  indanthrene  dyes,  but  due 
to  the  lack  of  time  and  the  difficulty  of  carrying  out  these 
reaction,  it  was  impossible.  In  case  of  all  compounds  the 
writer  attempted  to  increase  the  yield  and  in  some  cases  was  success, 
ful . 

It  might  be  v/ellto  state  here  that  these  condensations  depend 
largely  on  temperature  control  and  upon  the  use  of  exact  q^uantities 
of  constituents.  The  latter  condition  is  necessary  in  order  to 
have  as  small  amount  of  impurity  in  the  final  product  as  possible, 
as  the  purification  in  most  cases  is  difficult.  The  products  used 
in  condensation  were  p-chlorophenol , p-bromophenol , p-dichloro- 
benzene , p-cresol,  toluene,  and  aniline. 


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I-HSTOHIGAL  PART 
Ciuinizarine . 

Tuinizarine  is  by  no  means  a new  compo'und.  This  compound  was 
first  obtained  R.  Grimm,  in  1873,  by  condensing  phthalic  anhydride 


with  q^uinol 


-OH 


However,  only  a small  fractional  yield  of  the  theoretical  yield 
was  obtained.  The  following  processes  have  been  patented, 

(1)  Prom  anthraq^uinone — (a)  a mixture  of  10  parts  of  anthra- 
cuinone , 10  parts  of  crystallized  boric  acid,  and  200  parts  of 
sulfuric  acid  is  heated.  An  energetic  action  sets  in  at  260-280  0. 
Sulfur  dioxide  is  evolved,  and  the  formation  of  q_uinizarin  is 
complete  in  a short  time. 


+ 3 


If  the  heating  is  continued,  purpurin  is  formed. 

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0 


The  complete  formation  of  q^uinizarin  is  ascertained  by  spectroscopic 
test  on  a sample  diluted  with  sulfuric  acid . The  mixture  is  pour- 
ed into  water  and  the  quinizarin  filtered  off.  If  necessary,  it 
can  be  purified  by  dissolvii'.g  it  in  allrali,  and  precipitating  vdth 
acid . 

(b)  Pourteen  parts  of  sodium  nitrite  are  added  to  200  parts  of 


cooled  sulfuric  acid  and  when  all  is  dissolved , 10  parts  of  anthra- 
quinone  and  10  parts  of  crystallized  boric  acid  are  added.  The 


1 


F 


3- 


mixture  is  stirred  and  heated  as  q^uickly  as  possible  to  280-230  . 

At  180-190  , the  reaction  takes  place,  T??hich  is  complete  after 
heating  for  two  to  four  hours  at  220-230  . When  cool,  the  mixture 
is  poured  into  Vvater,  the  vhiole  boiled  to  decompose  the  boric  ester 
v/hioh  is  first  formed,  and  the  q.uinizarin  is  filtered  off.  Al- 
ternatively gaseous  nitrous  acid  can  be  passed  into  a solution  of 
10  parts  of  anthraquinone  and  10  parts  of  boric  acid  in  200  parts 
of  sulfuric  acid,  and  the  v/hole  is  heated  to  220-230  until  the 
solutf 


(o)  Ten  parts  of  sodium  nitrite  are  slovay  added  to  120  parts 
of  sulfuric  acid,  followed  by  7 parts  of  anthraquinone  and  1.6 
parts  of  mercuric  sulfate,  and  the  mixture  is  heated  until  at  180  , 
the  mass  is  brownish  red.  The  temperature  must  not  be  allowed  to 
rise  above  tnis  point.  When  cool,  the  mass  is  poured  into  water, 
the  precipitate  dissolved  in  sodium  hydroxide  solution  and  boiled 
for  half  an  nour , v/nen  the  solution  is  filtered  from  any  unchanged 
anthrac[uinone  ano  then  acidified  to  obtain  Q_uinizarin. 

( 2 ) From  er/throhydroxanthraq^uinone  , (l-hydroxyanthraquinone  ) 
Twenty  parts  ox  sodium  nitrite  are  dissolved  in  600  parts  of  sulfuric 
acid,  and  30  parts  of  boric  acid  and  then  30  parts  of  erythrohydroxy- 
anthraquinone  are  added.  The  mixture  is  heated  to  180-200  until 
a spectroscopic  test  shows  no  increase  in  the  amount  of  quinizarin. 

xhe  mass  is  cooled,  diluted  with  v/ater,  boiled,  and  the  quinizarin 
filtered  off. 


(3)  li'rom  phthalic  anhydride  and  p-chlorophenol . Eighty  parts 
of  phthalic  anhydride,  20  parts  of  Ix)  ric  acid  and  23  parts  of  p- 
chlorophenol  are  mixed  v/ith  400  parts  of  sulfuric  acid,  and  the 
mixture  is  heated  for  three  hours  at  150  . The  temperature  is  then 
raised  to  180-200  and  lept  at  this  point  until  the  amount  of 
quinizarin  no  longer  ire  reuses.  On  cooling  the  mass  is  poured 
into  twenty  times  its  q^uantity  of  water,  and  the  quinizarin  is 
filtered  off.  It  is  purified  hy  extraction  with  a large  quantity 


The  yield  is  70-80fo  of  the  theoretical.  Alternatively,  a solution 
of  60  parts  of  p-chlorophenol  in  200  parts  of  fuming  sulfuric  acid 
(containing  20^  of  sulfur  tri oxide)  is  heated  to  130-140  until  a 
sanq^le  , when  added  to  a 12^^  solution  of  salt,  gives  no  precipitate, 
showing  the  formation  of  p-chlorophenoldisnAfuric  acid.  T v/o 
hundred  parts  of  sulfuric  acid,  40  parts  of  boric  acid,  and  80  parts 
of  phthalic  arihydride  are  now  added  and  the  mixture  is  heated  as 
described  above.  After  some  time,  dark  blue  crystals  of  the  ester, 
*^14%^4*^^3^2^3  separate  out.  \lheu  the  quantity  of  this  no  longer 
increases,  the  mass  is  cooled,  and  the  ester  filtered  on  an  asbestos 
filter,  washed  with  sulfuric  acid  (60  Be'),  and  finally  with  ice 
water.  On  boiling  it  v/ith  water  or  sodium  carbonate  solution,  it 
is  converted  into  quinizarin. 

(4)  Erom  purpin.  To  tv/enty  parts  of  purpin  and  7 parts  of 
boric  acid  was  added  30  parts  of  concentrated  sulfuric  acid,  and 
this  was  stirred.  ’.7hile  stirring  strongly,  5 parts  of  aluminium 


5- 

powder  was  added,  and  the  temperature  kept  belov/  50  . Vifhen  the 
solution  turned  golden,  the  mixture  was  poured  into  water,  and 
filtered  off,  and  dried. 

(5)  From  1-4,  diohloroanthraq,uinone . Forty  parts  of  1-4 

dichloroanthraq_uinone  was  mixed  with  IOC  parts  of  concentrated 

sulfuric  acid  (10^  30g),  and  5 parts  of  boric  acid  at  200  0,  It 

was  then  poured  into  water  and  filtered. 

-d 

Mo  ^6 

^ +T  + H3BO3  ^ 

(6)  From  1-4  chloroxyanthraquinone . Ten  parts  of  1-4  chloro- 
oxyanthraq^uinone  was  mixed  vlth  50  parts  of  oleum  (20^),  and  50 
parts  of  sulfuric  acid  of  66  Be'.  Then  5 parts  of  boric  acid  was 

was  e.on,^]et& 

added,  and  the  temperature  kept  at  100  until  formation  of  quinizariij)? 
This  concludes  the  work  w^hich  has  been  carried  out  on  the  sjuithesis 
of  ouinizarin  up  to  this  time. 

P-chloroxyanthraquinone . 

P-chloroxyanthraquinone  , a derivative  of  anthraq_uinone  has 
been  prepared  by  tv/o  methods,  which  have  been  patented. 

(1)  From  1-oxyanthraq^uinone . (a)  Ten  parts  of  1-oxyanthra- 
quinone  was  mixed  with  60  parts  of  v*ater  and  stirred  until  a stiff 
paste  v/as  formed.  Then  400  parts  of  sulfuric  acid  (60  Be')  are 
added  and  heated  at  115-120  G.  After  stirring  a long  time,  a 
solution  of  60  parts  of  potassium  chlorate  in  water  v/ith  60  parts 
of  hydrochloric  acid  was  added,  and  the  temperature  kept  at  110-115. 
The  mixture  was  then  poured  into  a large  volume  of  v/ater  and  pure 
gold  needles  settled  out.  (b)  Ten  grams  of  hydroxyanthraquinone 

was  treated  with  50  grams  of  acetic  acid  (25^)  and  8 grams  of  sodium 


6- 


chlorate.  The  mixture  was  kept  at  a temperature  between  80-100  , 
and  5 grams  of  hydrochloric  acid  (15^)  was  added.  The  mixture 
was  poured  into  a large  excess  of  v/ater,  and  the  p-chloroxyanthr- 
quinone  precipitated  out  in  golden  needles. 


P-bromoxyanthraquinone  has  been  prepared  by  only  one  method 
up  to  this  time.  This  process  is  patented  under  D.  R.  ?.  131403, 
Ten  parts  of  erythroxyanthraquinone  was  placed  in  SCO  parts  of 
acetic  acid,  and  a solution  of  10  parts  of  sodium  bromate  was  added. 
The  solution  was  stirred,  and  25  parts  of  hydrobromic  acid  of 
specific  gravity  1.49  v/as  added,  and  then  V/armed  for  one  half  hour. 
After  cooling  it  was  poured  into  water,  and  filtered. 


2-methyl  anthraquinone  vdiich  is  of  importance  in  dying,  has 
been  prepared  first  and  then  converted  into  the  carbonic  acid 
of  anthraquinone . The  method  v/hich  is  patented  is  as  follows. 
Fifty  grams  of  phthalic  anhydride  and  20  grams  of  toluene  are 
mixed  together,  and  100  grams  of  powdered  AlGl^  are  added.  HGl 
is  evolved,  and  the  mixture  becomes  warm.  After  6 hours,  v/ater 
is  added,  excess  of  toluene  is  distilled  off  in  a current  of  steam, 
and  the  aqueous  solution  poured  off.  The  cake  precipitate  in  the 
bottom  is  made  alkaline  v/ith  sodium  carbonate,  steam  passed  in  for 
4 or  5 hours,  and  the  v/hole  filtered.  The  filtrate  is  acidified 
whereby  2-p-toluoyl  benzoic  acid  (m.p.  146)  is  precipitated. 


P-bromoxyanthrapuinone . 


2-methyl  Anthraquinone . 


o 


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7- 


This  is  treated  with  9 parts  of  f-uming  sulfuric  acid  (20^ 
and  heated  on  the  water  hath  for  on  e and  one-half  hours.  Then  it 
is  poured  into  water  and  2-methyl  anthraq^uinone  is  ohtained-pale 
yellow  needles,  m.  p.  177,  and  soluble  in  acetic  acid. 

To  10  parts  of  the  2-p-toluoyl  benzoic  acid  mix  200  parts  of 
water  and  dissolve  with  sodium  nitrate  and  then  added  to  a solution 
of  potassium  permanganate,  and  heated  for  one  hour  on  the  steam  bath. 
Then  add  bisulfite  solution  to  get  rid  of  excess  permanganate  and 
filter.  White  needles  crystallize  out,  v/hich  melt  at  234  , The 
products  can  be  crystallized  from  alcohol. 


This  product  is  treated  v/ith  200  parts  of  sulfuric  acid  (66  Be' 
f 0 r a few  hours  at  150-180,  and  the  condensation  results.  The 
melting  point  is  284. 

P-dichloroanthraquinone . 

The  above  mentioned  compound,  has  been  preparec  by  convertiiig 
dichlorophthalic  acid  into  dichlorobenzox^/benzoic  acid,  and  that 
into  dicliloroanthraquinone  • This  is  the  only  method  Vvh.ich  is  given 
in  the  literature , and  all  compounds  which  have  p-dichloroanthra- 
quinone  as  these  have,  refer  to  the  above  method  of  prepara.tion . 

Indanthrene  Byes . 

Vat  dyes  are  classified  in  the  following  manner. 

(a)  The  thioindigo  class  derived  from  indigo  by  replacing  the 
KH  group  by  sulfur  atoms.  For  example,  thioindigo  red,  thioindigo 
scarlet,  helindone  fast  scarlet,  and  helindone  brown.  All  these 


[T 


8- 


dyes  must  be  enQ)loyed  for  cotton  and  wool. 

(b)  The  Giba  colors  are  either  brominated  irjdigo  or  derivatives 
of  the  thioindigo  class.  Most  of  the  Giba  class  of  dyes  may  be 
applied  equally  well  to  animal  and  vegetable  fibre.  A few  examples 
of  this  class  are  Giba  heliotrope,  Giba  Green  G and  Giba  violet. 

(c)  The  indanthrene , algole  and  sencole  and  Gibanone  colors 
have  no  chemical  connection  with  indigo,  but  are  mostly  related  to 
anthraquinone . They  require  a large  amount  of  potassium  hydroxide 
to  the  hydrosulfite  vat  and  therefore  are  unsuited  for  use  with  the 
animal  fibre.  It  is  this  class  of  dyes  v/hich  I wish  to  give  the 
historical  background. 

One  of  the  most  important  developments  in  recent  years  has  been 
the  production  of  a series  of  dyes  known  as  the  indanthrenes , a 
series  of  dye  stuff  derived  from  anthrquinone  and  possessing  ex- 
ceptional fastness  to  light  and  to  cleansing  agents,  such  as  boiling 
soap,  and  chlorine . Although  first  discovered  in  1901,  by  H.  Bohn 
of  the  Badische  Anilin  und  ooda  Pabrik,  these  dyes  are  now  manufact- 
ured in  twelve  or  thirteen  shades,  covering  the  whole  range  of 
colors  from  red  to  blue.  On  account  of  their  fastness,  they  are 
largely  employed  in  the  dyeing  of  Sundour  and  other  guaranteed 
fadeless  fabrics.  The  first  and  one  of  the  most  important  dyes, 
indanthrene  blue,  was  obtained  by  fusing  of  an  amino  derivative  of 
anthraquinone  with  caustic  alkali,  whereby  tv/o  molecules  of  anthra- 
quinone  v/ere  caused  to  join  up  and  yield  indanthrene  blue. 


9 


It  is  necessary  here  to  take  up  the  action  of  this  compound  in  order 
to  have  a clear  uaderstanding  of  this  series  of  dye  stuff.  If  the 
preparation  of  indanthrene  is  carried  out  in  the  presence  of  reduc- 
ing agents,  there  is  obtained  a large  amount  of  coloring  matter, 
which  is  no  good  and  very  soluble  in  quinoline.  Therefore,  this 
reaction  should  be  carried  out  in  the  presence  of  oxidizing  agesnts. 
Indanthrene  on  reduction  does  not  give  2-amino-anthraquinone  or 
a reduction  product  of  this  substance.  Therefore,  it  is  not  an 
azo  derivative  and  there  is  no  free  amino  group.  They  have  taken 
place  in  the  condensation,  Alizarin  is  also  formed,  which  suggests 
the  joinhig  of  two  anthraquinone  residues  through  agency  of  the 
hydrogen  atom  in  the  ortho  position,  and  the  amino  group.  Tv/o 
possible  formulae  are; 


Indanthrene  can  not  be  converted  into  a diamine  on  reduction  and 
therefore,  can  not  have  ortho-formula . Reduction  of  indanthrene 
by  sodium  h3rposulfite  in  the  presence  of  alcohol  gives  a blue  vat 
which  contains  al-kali  salts  of  the  dihydro  derivative  in  solution. 
The  vat  v/ith  zinc  dust  gives  a yellowish-brown  which  is  also  oxidized 
by  the  air  to  indanthrene.  The  complete  reduction  of  indanthrene 
with  phosphorus  and  hydroiodic  acid  at  El£  leads  to  the  anthrazine . 

Indanthrene  is  a v/eak  base,  and  forms  salts  with  strong  acids, 
which  are  dissociated  with  water.  The  two  hydrogens  of  the  imido 


10- 

group  are  readily  removed  "by  oxidation  and  the  base  is  transformed 
into  a yellov/ish  green  azine  , azine  is  readily 

reduced  to  indanthrene . The  entrs-nce  of  halogen  on  indanthrene 
rings  turns  the  shade  toward  green.  Other  important  dyes  of  this 
series  which  are  known  are  indanthrene  blue  G.  0.,  antlirafluvine , 
indanthrene  yellow,  fluvoanthrene , and  indanthrene  grey. 

Until  recently  none  of  these  dyes  have  been  manufactured  in 
England,  but  in  the  year  1918,  indanthrene  blue  yips  manufactured 
by  British  dye  limited,  and  placed  on  the  market  under  the  name 
of  alizarine  delphinol.  This  series  of  dyes,  and  also  the  sulfur 
dyes  derived  from  anthraq_uinone , belong  to  what  are  called  by 
dyers,  vat  dyes.  The  vat  dye  stuff  from  the  viev;  point  of  the 
chemist  are  classified  into  three  groups.  Anthracene  dyestuff, 
indigoid  dyestuff,  and  sulfide  vat  dyestuff.  These  classes  in- 
cluded the  fastest  of  coal  tar  dyestuffs  at  present  known, 
though  it  is  necessary  for  the  reader  to  realize  that  if  a dyestuff 
belongs  to  the  vat  series  it  is  not  necessarily  possessed  of  the 
same  fastness  of  the  best  members  of  this  class.  However,  these 
are  insoluble  in  water.  Owing  to  the  insolubility  of  these  dyes 
in  water,  it  is  no  possible  to  prepare  dye  baths  in  the  ordinary 
manner,  and  for  the  purpose  of  dyeing  a less  direct  nelhod  must  be 
employed.  In  using  these  djT-es,  advantage  is  taken  of  the  fact 
that  tney  are  comparatively  readily  reduced  to  compounds  (so-called 
leuco  compounds)  which  are  soluble  in  alkalis.  The  naterial  to  be 
dyed  is  therefore  dipped  in  the  alkaline  solution  of  the  leuco 
compound,  now  generally  produced  from  the  dye  by  reduction  with 
sodium  nydrosulfite , v/nich  is  readily  taken  up  by  both  the  anii!ial 
and  vegetable  fibres.  On  exposing  the  material  to  the  air,  the 


■J . •■>-•- 


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11- 

oiiginal  dyestuffis  produced  in  the  fibre  in  an  exceedingly  fast 
form,  owing  to  the  oxidation  of  the  leuco  compound  by  the  atmos- 
pheric oxygen.  Sometimes,  the  leuco  compound  of  the  dye  is  color- 
less, or  very  faintly  colored,  but  in  other  cases,  as  in  the  case 
of  indanthrene  dyes  , the  leuco  compound  may  have  a very  marked 
color,  which  is  generally  different  from  that  of  the  original  dye- 
stuff. Although,  formerly  vat  dyeing  was  a somewhat  difficult  and 
uncertain  process,  it  has  now  been  rendered  as  easy  and  as  simple 
as  eyeing  from  the  ordinary  bath.  The  success  of  good  dyeirig 
v/ith  this  class  of  dyes  depends  upon  correct  temperature,  even 
dyeing,  absence  of  unnecessary  oxidation,  and  presence  of  sufficient 
alkali  and  hydrosulfite  to  keep  the  dyestuff  in  solution. 

In  conclusion,  this  briefly  covers  the  v/ork  dene  on  the  in- 
danthrene series  of  dyes  up-to-date,  and  leaveo  wide  field  for 
the  chemist  of  the  future  to  develop. 


v'-VyVS'X'^^  ■ ' ". '''  ' ' • ^ ' 

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v , ■‘iv . 


12- 


THECREIIGAI  PART 

The  theory  involved  in  the  condensation  reaction  is  very 
simple.  The  phthalic  anhydride  gives  np  ah  oxygen  atom  which 
combines  v/ith  two  hydrogens  from  the  ring  of  the  benzene,  and  its 
derivatives  or  with  the  hydrogen  from  the  ring  of  the  phenols  or 
their  derivatives.  Por  example,  if  phthalic  anhydride  is  condens- 
ed with  G^qHqO  in  the  presence  of  sulfuric  acid,  or  other  condens- 
ing reagents,  the  following  reaction  ensues. 


o f 


The  most  of  these  reactions  take  place  in  two  stages.  The 
first  product  which  is  obtained  is  the  acid  and  then  on  heating 
higher,  water  is  split  out,  and  the  carbon  atom  of  the  carboxyl 
group  is  Joined  to  the  ring.  The  condensation  reagents,  such  as 
AlGl  , sulfuric  acid,  carbonyl  chloride,  forma.ldehyde , A1G1_  in 

GS  , and  ferric  chloride  all  are  good  to  take  up  the  water. 

2 

The  theory  involved  in  dyeing  in  vats  rlth  the  dyes  msde  by 
the  use  of  these  condensation  products  spoken  of  above,  may  be 
referred  to  the  capacity  of  the  dyes  of  forming  leuco  compounds  of 
v/eakly  acid  properties  v.lnch  possess  an  attraction  for  the  fibre, 
and  are  readily  oxidized  by  air.  In  case  of  the  vat  colors  belong- 
ing to  the  anthraquinone  class  this  property  is  attributed  to  the 
presence  in  the  molecule  of  carbonyl  groups,  v/hich  by  alkalirie  re- 
ducing agents,  are  converted  into  -G-OH  groups,  or  their  soluble 

H 

alkaline  salts. 


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13- 


exisrilis:htal  part 


PhtAalic  anhydride  v/as  used  in  all  the  reactions.  It  served 
as  a foundation  on  \^ich  to  attach  other  compounds  in  order  to  form 
derivatives  of  anthraquinone . Phthalic  anhydride  is  made  commerci- 
ally by  oxidizing  naphthalene  in  the  presence  of  mercuric  salts 
with  sulfuric  acid.  The  oxidation  is  thus  indirectly  brought 
about  by  the  atmospheric  oxygen. 


The  crude  anhydride  is  separated  from  sulfuric  acid  by  decanting 

and  then  is  further  separated  by  cent rifuging,  and  is  washed  free 

from  acid.  The  product  is  dried  and  purified  by  resublimation  in 

a pan  mechanically  stirred  and  heated  over  a coke  fire. 

The  first  condensation  reaction  run  was  with  toluene,  a coal 

tar  product  which  is  obtained  in  the  light  fraction  of  oil  on 

distillation.  Ten  grams  of  phthalic  anhydride  and  EO  grams  of 

toluene  was  placed  in  a flask  and  15  grams  of  i-lGl_  w'as  added. 

3 

This  mixture  was  heated  at  first  upon  the  steam  bath,  and  afterv/ards 
by  flame  until  all  the  hydrochloric  acid  gas  was  given  off.  The 
contents  were  then  cooled,  and  poured  into  two  liters  of  water. 

The  pmducts  were  recrystallized  from  toluene,  nixed  with  alcohol 
and  the  yield  was  only  11^  of  the  theoretical  yield.  The  above 
mentioned  conditions  are  the  best  v/hich  I found  upon  different  runs. 
If  temperature  is  kept  too  high,  and  if  it  is  heated  too  long,  one 
obtains  a black  tarry  substance. 


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14- 


This  compound,  v/hich.  is  E-p-toluoyl  benzoic  acid,  melted  at 
145-147  . The  --p-toluoyl  benzoic  acid7as  heat  at  120  with 

concentrated  sulfuric  acid  for  nine  hours,  and  then  the  temperature 
be  raised  to  150  for  2 hours.  After  cooling  the  mixture  was  pour- 
ed into  water  and  recrystallized  from  alcohol.  The  yield  of  2- 
methyl  anthraq_uinone  v/as 


It  crystallized  in  yellow  needles  and  melted  at  175-176  . 


The  2-methyl  anthraq_uinone  was  next  oxidized  by  heating  it  with 
sulfuric  acid  and  potassium  dichromate  at  75  and  finally  raising 
the  temperature  to  95  ,and  heat  for  12  hours. 


The  yield  was  only  of  the  theoretical  yield.  The  product  was 
crystallized  from  alcohol,  and  the  melting  point  was  282  . On 

varying  the  condition,  I was  unable  to  produce  a larger  jT-ield.  The  1 
supply  of  toluene  was  exhausted  at  this  time,  so  I left  this  phase 
of  the  problem  and  did  not  return  to  it.  j 

The  next  reac'rion  which  I studied  was  the  reaction  of  p-cresol 
and  phthalic  anhydride  in  the  presnece  of  concentrated  sulfuric  acid. 
Five  parts  of  phthalic  anhydride  v/us  placed  in  a round  bottom  flask 
and  two  parts  of  p-cresol  was  added  with  15  parts  of  concentrated 
sulfuric  acid.  This  mixture  was  heated  at  130  for  12  hours. 

Then  betv/een  180-195  for  a few  hours  longer,  and  finally  cooled 
and  poured  into  water.  This  was  filtered  and  dried.  This  compound 


15- 

was  not  purified  because  all  of  the  soft  tarry  residue  could  not  be 
removed.  The  dried  product  was  placed  in  a distilling  flask  and 
zinc  dust  was  added  and  the  ^reduced.  The  contents 

on  heating  would  give  off  a dense  cloud  of  gas,  and  then  clear  up 
for  a minute,  and  then  another  cloud  of  gas  v/ould  be  given  off. 
Finally  the  heat  had  to  be  removed  in  order  to  prevent  the  flask 
from  breaking.  There  was  considerable  heat  evolved  within  the 
flask.  The  flask  was  cooled  and  the  contents  was  nothing  but  zinc 
dust  and  black  crumb  like  substance  which  was  carbon.  The  yield 
by  this  method  is  only  5^,  and  the  product  formed  is  alpha  methyl 
anthracene.  On  oxidizing  the  alpha  methyl  anthracene  with  cromic 
acid  in  the  presence  of  acetic  acid,  alpha  anth raq^uinone  carbonic 
acid  -is  obtained. 


These  reactions  are  hard  to  carry  out.  Therefore,  the  temperature 
should  be  carefully  v/atched  and  controlled. 

The  condensation  of  phthalic  acid  v/ith  the  p-halogen  derivative 
was  the  next  field  of  research  in  which  I entered.  In  order  to 
run  tnis  series  of  reactions,  I was  forced  to  prepare  my  phenol 
derivatives.  Formerly,  p-chlorophenol  v/as  prepared  by  chlorination 
of  phenol  for  IE  hours  at  temperatuie  of  melting  ice.  This  re  actio;:, 
was  carried  out,  but  it  was  found  that  the  yield  was  very  small. 


/ * * ■ y ' * '•  ^ T jj'  ' ’ * * ‘ ^ ' 


,:""v/ 


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16- 


The  products  v/ere  riDstly  phenol  and  the  ortho-chlorophenol . This 
reaction  was  handled  under  various  conditions,  and  various  lengths 
of  time,  but  the  yield  was  alv/ays  small.  The  phenol  had  a tendency 
to  solidify  in  the  ice  solution  and  stop  the  passage  of  the  chlorine 
gas.  However,  this  solidification  v/as  prevented  somewhat  by  use 
of  mechanical  stirrers  to  keep  the  p-enol  in  motion.  But  still 
the  yield  remained  low.  Phenol  was  dissolved  in  carbon  tetra- 
chloride, and  thai  chlorinated  for  IE  hours,  and  it  v/as  found  that 
the  yield  by  this  method  was  30^.  So  this  proved  also  unsatisfact- 
ory, although  it  v/as  the  hipest  yield  I had  yet  obtained. 

I found  out  that  by  treating  phenol  with  SOgCl^,  I could  get 
a yield  of  51^^  of  p-chlorophenol . The  SOgClg  was  irade  by  passing 
sulfur  dioxide  £uid  chlorine  alternatively  into  10  grams  of  pulver- 
ized camphor  dipped  into  an  ice  bath.  The  SOgClg  v/as  distilled 
over  on  the  steam  bath. 


However,  the  most  satisfactory  means  of  preparing  p-chloropheno. 
was  by  adding  3 cc.  of  v/ater  to  every  50  grams  of  phenol  added,  and 
allow  chlorine  gas  to  pass  through-the  solution  until  a v/hite  solid  | 
v;as  obtained.  This  v/as  then  distilled  and  the  fraction  from 
S17-ES5  v/as  collected.  The  yield  was  85^  of  the  theoretical  yield. 
The  p-chlorophenol  melts  at  43  C, 

Pifteen  parts  of  phthalic  acid  v/as  placed  in  a round  bottom 
flask  and  13  parts  of  p-chloro  ^henol  was  added.  Eight  parts  of 

sulfuric  acid  was  added,  and  the  mixture  heated  at  120  for  10  hours. 
Then  the  temperature  v/as  raisecl  to  180-190  for  two  hours,  and  finally 


17- 


poured  into  water.  !T  he  yield  hov/ever,  v/as  only  12^^.  This  same 


glacial  acetic  acid,  were  used,  hut  the  yield  was  even  less. 
Aluminium  chloride  was  not  used  because  that  is  too  expensive. 

The  best  yield  which  I obtained  was  by  heating  13  parts  of  p-chloro- 
phenol  with  15  parts  of  phthalic  anhydride  in  the  presence  of  con- 
centrated sulfuric  acid  for  3 hours  at  150  . Then  the  temperature 

was  raised  to  180-190  for  a few  hours  and  finally  it  v/as  poured 
into  20  ti'nes  its  volume  of  water.  The  p-chlorcxyanthraquinone 
precipitated  as  golden  needles.  The  compound  v/as  identified  in  the 
following  manx.er.  It  v/as  fused  v/ith  sodium  and  it  gave  the  halide 
test  after  it  had  been  purified  by  dissolving  in  alkali  and  being 
precipitated  v/ith  acid.  It  also  gave  a green  compound  on  heating 
with  primary  amines  (aniline)  which  later  turned  brown  w^hen  the 
temperature  v/as  raised.  V/hen  the  product  was  fused  in  a crucible 
it  was  converted  into  q_uinazarine . It  crystallized  in  red  needles 
and  had  a melting  point  of  193  G.  The  yield  by  this  method  is  18.5 


P-chlorophenol  v/as  replacedby  p-bromophenol  and  the  reaction 
run  under  the  same  conditions  as  it  was  before  , and  p-bromoxyanthra- 
quinone  v/as  obtained.  It  formed  crystals  upon  pouring  into  water, 
in  the  form  of  brov/n  needles.  The  yield  was  22^.  Hov/ever,  the 
reaction  was  not  used  to  any  great  extent  on  account  of  the  cost 
of  p-broraophenol . ^^14" 


0 


18- 

?his  is  crystallized  by  dissolving  in  allcali  and  precipitating  with 
acid . 

A similar  reaction  was  run  vilth  aniline  in  place  of  p-chloro- 
phenol.  The  concentrated  sulfuric  acid  causde  the  sulfonation  of 
phenol  which  prevented  the  isolation  of  any  amino -an th raq^u inone  . 
However,  a small  yield  of  amino-anthraq^uinone  was  obtained  by  reg- 
ulating  the  reaction  as  in  the  case  of  p-chlorophenol , but  using 
Alolg  dissolved  in  instead  of  sulfuric  acid  as  the  condensing 
agent.  It  is  very  difficult  to  purify  the  amino -anth raq^uinone  , 
and  I found  no  means  v/hich  proved  satisfactory. 

The  last  reaction  Y/hich  I made  a study  of  was  the  condensation  . 
of  p-dichlorobenzene  with  phthalic  anhydride.  Ten  parts  of  phthal- 
ic  anhydride  v/as  heated  at  110  with  10  parts  of  dichlorobenzene  in 
the  presence  of  8 parts  of  sulfuric  acid.  After  10  hours,  the 
temperature  was  raised  to  180-190  , and  kept  there  for  a few  hours, 
and  then  poured  into  water.  This  reaction  v/as  run  similarly  to  the 
reaction  described  by  Dr.  7/.  a,  Noyes  in  his  laboratory  manual  for 
the  preparation  of  oxyanthraq_uinone  . The  yield  Y/as  negative,  and 
the  reaction  was  discarded  for  a time. 

Finally,  15  parts  of  p-dichlorobenzene  Y/as  treated  with  10 
parts  of  boric  acid  and  100  parts  of  concentrated  sulfuric  acid, 
fifteen  parts  of  pntnalic  annydride  v/as  then  added,  and  thoroughly 
mixed.  The  tempeiature  Y/as  kept  at  150  for  3 hours,  and  then 
raised  to  180-190  for  one  hour.  The  mixture  was  poured  into  2 
liters  of  v/ater,  and  purified  by  dissolving  in  alkali  and  precipitat. 

ing  with  acid.  The  yield  was  15.5  grams  fro  20  grams  of  phthalic 
anhydride  and  20  grams  of  dichlorobenzene.  T^is  was  ten  grams 
more  tirnn  Y/hen  the  reaction  was  run  without  the  use  of  boric  acid. 


VT-^V  y 


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19- 


This  product  thus  obtained  melted  at  17E  . TJiis  product  v/as  then 
heated  with  9 parts  of  concentrated  sulfuric  acid  1C$«  SO^,  for 
four  hours  at  190-195  , and  then  poured  into  water.  A product 
was  obtained  which  gave  a test  for  halides  and  had  a melting  point 
of  185  , which  corresponds  to  the  one  which  is  given  in  the  liter- 
ature for  CQ^^H^CgClg. 


I was  forced  to  stop  my  research  before  I v/as  able  to  find  a good 
means  of  purifying  it. 

In  conclusion  of  my  experimental  work,  I obtained  a 70^  yield 
of  phthalic  acid  by  heating  phthalic  anhydride  with  concentrated 
sulfuric  acid  for  12  hours  at  110-115  G, 


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SmOvERY  AND  CONCLUSION 

The  condition  for  condensation  of  the  different  products  with 
phthalic  anhydride  seems  to  work  best  when  temperature  is  kept  for 
three  hours  at  150,  and  then  raised  to  180-19C,  for  a few  hours, 
using  sulfuric  acid  as  the  condensing  agent . In  all  cases  at  least 
a small  yield  v/as  obtained,  and  therefore  it  seems  probable  that  on 
varying  conditions,  a satisfactory  yield  could  be  obtained.  The 
presence  of  boric  acid  tends  to  increase  the  yield  and  make  the 
reaction  run  smoother.  The  most  promising  reaction  is  the  con- 
densation of  p-dichlorobenzene  with  phthalic  anhydride  in  the 
presence  of  boric  acid  and  concentrated  sulfuric  acid.  Also,  the 
condensation  of  aniline  with  phthalic  anhydride  seems  to  be  possible 
and  this  would  also  furnish  an  interesting  problem  to  work  on.  It 
mi^t  be  said  finally  that  the  work  on  tliese  intermediates  is  not 
complete  by  any  means,  but  they  are  developed  to  the  stage  where  one 
can  take  a hold  of  them  and  by  careful  regulation  of  temperature, 
and  upon  varying  the  conditions,  be  able  to  produce  a satisfactory 
yield.  The  yields  with  the  different  compounds  varied  all  the  way 
from  5 to  42^.  But  in  the  case  of  the  preparation  of  p-chloropheno! , 
a yield  of  855«  was  obtained,  and  the  product  was  a very  good  one. 
Also,  phthalic  acid  was  obtained  from  phthalic  anhydride.  The 
yield  was  70^  of  the  theoretical  yield. 

It  is  not  worth  while  to  discuss  here  again,  the  condition  which 

arose  in  the  reactions  as  they  were  discussed  in  the  experimental 

if 

part.  It  may  be  said  in  conclusion  that  this  work  has  proved 
nothing  of  startling  importance , it  has  at  least  showed  that  benzene 


and  its  derivatives  and  phenol  and  its  derivatives  v;ill  combine  with 
phthalj c anhydride  to  a certain  extent,  and  that  the  extent  of  it 

-iv.  ’-"^ndo  n-pi  -Piitmgis  faivotiti  gutn 


21- 


BIBIIOGRAPHY 

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